Vat dyestuffs and process of making same.



UNITED STATES Parana l KARL SCHIRMACHER AND ARTHUR VOSS. OF HljCI-IST-GN-TH? ASSIGNORS TO FARBWERKE VORM. MEISTEB LUCIUS (l1 BE.

ON-THE-MAIN, GERMANY, A CORPORATION OF GERMANY.

VAT DYESTUFFS AND PROCESS OF MAKING Silwiilil.

No Drawing.

To all whom it may concern Be it known that We, KARL Summing-inn, P11. 1)., chemist, and ARTHUR Voss, Ph. D., chemist, citizens of the Empire of Germany, residing at Hochst-on-the-itlain, Germany, have invented certain new and useful Improvements in Vat Dyestuffs and Processes of Making Same, of which the following is a specification.

We have found that the coloring matters of the general constitution:

wherein Ar A1 Ar stand for aryl resi dues which may be substituted in Whatever manner, are valuable vat dyestuffs, dyeing cotton on reduction with alkaline hydrosulfite tints of great variety and of excellent fastness. These new dyestuffs are obtained by heating a-halogen-substituted anthraquinones with the salts of the aromatic glycins, converting the resulting anthraquinonyla-arylglycins of the general formula:

if ll with agents capable v of eliminating water.

Specification of Letters Patent.

Application filed February 25, 191%. Serial No. 829,876.

The dyestufis thus obtail the first mentioned gene" may be denominated isatai are difficultly soluble in T of the organic solvents the vat various tints of The following exam preparation of the sim 1 threnes of this series:

Example: parts of :rchloanthraqninone are Well mixed with :20 parts of car fully dried potassium phenylglycin and 1 part of cuprous chlorid and heated to boiling with amylalcoliol, While stirring,'un-

til the intensity of the re blue solution no 1 rig-e curs after some hours. removing the amylalcohol tracted with a hot soluti bonate whereupon the no product dissolves to a violet so men. 4 precipitated by an acid and r crystal from chloroform, this product forms lol red crystals, when crystallized from glacial acetic acid, dark violet needle-like crystals melting at 196-197 C. The analysis shows that this product constitutes an o-anthraquinonylphenylglyein, which probably has the formula:

It dissolves in cone. sulfuric acid to a yellow solution, in oleuni (Qflfilbstrengtl) to a blue solution, in chlorosulionic acid to a green solution.

36 parts of the aicresaid eanthraquinonyl- N-phenylglycin, 400 parts of alcohol and 10 parts of concentrated; sulfuricacid are boiled for 5 hours in a reflux apparatus and most part of the alcohol is then distilled oil. On cooling, the mass solidifies into a darkred crystalline cake. After filtering, was ing with diluted alcohol, pressing and dry ing auproduct is obtained which loans a dark red "powder soluble in alcohol to a red solution irom which t crystallizes as red small needles. parts of the ester thus tints.

I with. a green fluorescence.

obtained are heated in an autoclave for two hours tc150 C., while stirring, 'With parts of caustic alkali and 100 -parts of xylene. After cooling, the Xylene is ex-. polled by means of steam, the remaining lye is, filtered and the brownish, fluorescent solotion is acidified by-means of a mineral acid. The resulting a-anthra-N-phenylpyr rolcarboxylic acid is precipitated as a powder of a yellow color. 'After filtering and drying it is freed from the slight impurities it may contain by extraction with benzene. The dyestufi' thus obtained dissolves in (11- luted solution of sodium carbonate to a yellow solution showing a beautiful yellowisht green fluorescence, and dyes wool and silk in a bath acidulated with acetic acid yellow It dissolves in concentrated sulfuric acid to a violet-red solution, in fuming sulv furic acid and chlorosulfonio acid to .a

claret-red solution with a slight fluorescence. In organic solvents it is difiicultly soluble It crystallizes from pyridin, assmall laminae of'a yellow color.

40 parts of the a-anthra N-phenyl-pyrrolcarboxylic acid above referred to are introduced at 0 G. into 150 parts of chlorosul:

ionic acid and this mixture is kept at theaforesaid temperature for 2-3 hours, i. -6. until a sample rendered alkaline no longer exhibits any fluorescence. The mass is then put on ice, the product which separates as red flakes is filtered off and extracted by trated sulfuric acid it'is soluble to adeep vidlet-red solution and gives with alkaline boiling with a strongly diluted solution of- When dry, the new body forms a alkali. reddish-brown powder and has the formula:

. co- I l which is difiicultly soluble in organic s01- vents. It dissolves most readily in pyridin with a reddish-brown color. In concenhydrosulfite a dark-blue vat which dyes cotton red tints.

. of great "fastness. i a In testiihony whereof, we a-ifix our s1gna- Having noffl described our inventiongwhat' we claim is: 1. As a new process, the manufacture of new vat dyestuffsof the isatanthrene series b" producing esters of he anthraquinonyla-arylglycins obtained from a: halogen anthraquinone and an aromatic glycin, trans forming them into the anthra-N-arylpyrrolcar'lioxylic acids by saponification I and jdehy dration, and treating the latter with bodies able to split off water.

2. As new products,' the vat dyestufis of the isatanthrene series having the general formula:

C0 0? Ar I l 7 f wherein Arfl iA'iand stand for. aryl residues; bel'ngiscan'ly soluble "in water i and inmost of the teirganic' hfents anddye ing. cotton 'fromj ie ivat ar ious tints of greatfastness. K LI; I I 3. .As a new product, the isatanthrene of being a reddish-,brown povfder diificultly soluble in water and in most of the organic solvents, readily soluble in' pyridin with a reddish-brown color, inconcentratcd sulv furic aci'd'with a deep reddish-violet color, 109

and yielding-with alkaline hydrosulfite a :1 dark-blue'. yat which dyes cotton red tints tu res in pi'esence of two Witnesses.

i KARL SCHIRMACHER. ARTHUR VOSS. Witnesses: v i JEAN GRUND, CARL GRUND.

. It is hereby certified that in Letters Patent- No. 1,123,390, granted January 5,- 1915, upon the application of Karl Schirmaeher mid ArLhui'Voss, 0i Hichet-onthe-Mein, Germany, for an improvement in Vet Dyestuffs and Processes; of Meking Seine, an error eppeers in the printedepeeifieation requiring corree'eien es folkiws: Page 1, lines 12-28, formula, for

and that the said Letters Patent sheuld be read \ilith this correct-ion therein fimt the same may confoi ni be the record of the ease in the Pa ten t Ofliee.

Signed and seaied this 7th day ofsepee nber, A; B., 1915.

' 5. 1". NEWTON,

Acting Commission? 0f PGf IZ58( 

